The synthesis and characterization of several C3v-symmetrically extended tribenzotriquinacenes (TBTQs) bearing six benzylic C1-tentacular functional groups at the arene periphery were reported. A new C3v-symmetrical hexakis(chloromethyl)-substituted TBTQ derivative was used as the key intermediate, and other derivatives were synthesized with high efficiency by either sixfold nucleophilic substitution reactions with phenols or sixfold FriedelCrafts alkylation reactions with various arenes.